Automatic measuring device for gaseous mixture analysis



March 22, 1932. D. R. L. FOLLET AUTOMATIC MEASURING DEVICE FOR GASOUSMIXTURE ANALYSIS Fild Nov. 8. 1927 2 sneetwsheei 1 March 22, 1932.

D. R. L. FOLLET AUTOMATIC MEASURING DEVICE FOR GASEOUS MIXTURE ANALYSISl'l'wl'l'lls'r Filed Nov. 8. 1927 2 Sheets-Sheet 2 IN VEN TOR 2x11@ 72.Z22/ef ATTORNEY Pamesa un,212,'` 1932( Y l uirssraf'rssfe LIQUIDE`so`oirrin. 'ANONYME reimr LETUDE 1& LEXPnoIrArron"'nnsjjinoonp 'spafter the reaction.L

lGaone-nfs' yoit-.Limusa ori rnnis, Enanos fAnmoirmtrdnnasnnne.nEvrCnfson ensn'ous-irrsnrunnnnnnirsis y n sAppuation' mee Nvemjer? s, i927, serial' up'- senses; and in r1-ansenayir; 1927.: u

f VThis .invention relates to an automatic :measuring device designedort 1f@ analysis of any gaseous mixture tlirouglifV absorption,combustionor any other reaction of one or :several of .Atlielge'seousmixture components, Vby measuring ,the residual volume subsisting Ynptli'e hitherto known automatic devices Yor gas analysis by measuring aresidual gaswLV leousfyolume, the operation is conducted in,"

vone of ,two Ways either the residual? gas is collected in a movableenclosure (for example a bell) connected with a `registering devicethrouglirigid members, sortliat the unavoidable inertia of tli-eregistering devices a cause of .error in the estimation` oftnetlieoretical equilibrium position of tlie enclosure and,

o Consequently,-in tlie measuring of the residual thereby H l y y L-renders my apparatus' or deviceesl'neeially volumeor else avmeasurement iis made as -for instance'by meansof a VHeat;o'ftlneleveldispl'aeements of a'liquid contain-ed in tube that communioateswvitlitlie residual gas, un- Y der suoli conditi ons that-to a variationintlie residualy gaseous volume tlierevwill colfespon'd a substantiallyequalfvariation of tlievolume occupied Within tlie tube by the liquid,in

YWliien case the tube must be given'a'sec'tion rsuiiieient yto vpermittlier float, or any other 'auch `like ter-:operating sontrivanee,` toAbe introduced tliereinto, Wliiehlimits the amplitude of the liquid leveldisplacements, ythaty isto saytlieracouraoy ofV the measuring. 'Y

This invention has orlone ofits obgects to "automatically register, by'means of afspecialy liydrostatic transmission, the measure of the`'residual gaseous volume'in suoli conditions that the volume variationsof the liquid' in tbe hydrostatic equilibrium tube containing the floatof the registering device can beinadej as ,great as required in respectof the` correspond- Ying volume variations of tlievresidualgasy in' themeasuring burette s'otliat acou'ra'o T is A 1). c 7 L a materiallyincreased, v,Said feature ser useable `ortlie purposes of analyzinggas-AV'eous ,inifturesjin VWblcli the residual volume is Very small,oigonftlie coiitraryrveryclose-to the initialvolume, as is tbe/case, forinstancml mmesmtivsf sur@ ,eases the purity stifle.

`condition fof 'vvliicliis desired to be asceruents to beremovedfromtliegaseous mixture n" aliquidi'sunsite treatment i ,Otheradvantages@ the miremos m11 als@ appear rkfurther von VIfrom theolloxving'gded scriptiona'kc A i Y n ,i

`My apparatus or device takes availloj tlie through a gasor,iiiverseloffa'gas through liquid, is impossible Witliinf a' capillarytube.v

nprder to maketlie invention quite clearly understood,r Ijvill' now fullf describe lreference :to the accompanying drawings, in `which: v

)Figure `1 illustrates, as an examplman embodiment ofadevice intendedfor measuring through, "ebSOIPiQMhG-swde @fruity ef commercialonygen.. af

f Figure 2 slioivspn `anei'ilarged- 4scale Va detail f Figures 3 Vandlllrepresent modifications easuring .burette which 'is .pa-rt `of tbe lliguredlfdeilice.'Y 1 n, s

0 is a contl ner provided Witligafside tube t comniunicatinv withtlieatmos here;

v`Bis a measuring burst-te `ivliereintotlie gas j its upper partterminatingin a secondxcapillary tube d. A capillary tube 0connects'tube Y per oart of which electrolytic copperltivist-smunication With the 4atmosphere v Y and` provided at its-upper paitwitlian overflow tube v exposed to atmospliericair.

.VS is a Uesliapedtube connecting 1tlie'lovver part of reserxfoirI@kkwith vessel R andthe verT tical branches o', which aref n a ,lengthVA ekwhich d'scliargesinto; a reservoir 'also fz aaai an sbsorpuoabureae L,matthew@ arey pressedfby means Qi afsprmg vvou.y The y vlovver Qartbfburette vL communicates zum@ .tuberwiihanfopen ab@ ,E in @0mlieu 1greater than the liquid height in the apparatus that measures thepressure of the operatinggas, of which more hereinafter. Y l

2, V3 and V4 are valves mechanically controlled from one and the samecam shaft (not shown) i which is rotated by a small electric motorthrough a lspeed reducing gear.

P1 vand P'fare draining cocks.

The rliquid or liquor with which the apparatus is provided in theexample under consideration is an ammonia solution the coinposition` ofwhich is Well known and whichy has the property of absorbing oxygen inthe presence of copper.

Previous to any measuring operation, I fill the siphon-shapedtube 8 withliquid of which the height in the vertical branches is greater than theliquid-height that measures the pressure of the operatiner gas. I begin`bycharging the apparatus with liquid, for which piirpose I proceed asfollows:

Through its central nozzle I till jar R with n. suitable amount ofammonia solution and I' shutv'alveV, lleaving open valves V1, V2

and Vs. Under the pressure (about 0.50` meterskof water) of yanoperating gas, for instance nitrogen, coming in through -valve V`aandhaving'no action on the liquid in the apparatus,y the liquid iscaused to rise in coni tainer r, tube t and burette B; the air containedin burette B is driven out through valve V1r while the liquid continuesrising. When said liquid has reached the levelof capillary tube c, Ishut valve V1 and the liqui Hows on through tube c, burette L, tubes T,E, e, reservoir F and tube S. Once requilibrium is established, I openrvalve V- and I shut valve V3, while V1v remains shut? and valve V2open;`the liquid in the apparatus then flows in the direction oppositethe above indicated one, driving through tube c part yof the aircontained in biiretteL, said part of air being thereby transferred intoburette B. The liquidceases to flow when hydrostatic equilibrium isestablished in the set E, T, L, c. d and B. I then repeatl the first ofthe above described operations, that is to say I open valve V"`.againand I shut valve V4 again, taking care to open also valve V1 again. Theportion of the air within burette L that was transferred into burette Bis thereby driven out through valve V1. As will be readily realized,when this double toandfro 'flow of the liquid throughout the apparatushas been effected two or three times, the

whole amount of air ycontained in burette L will have beendriven out,while burette B is Y the only one that still contains someaii", and

the whole set consisting of tube c, burette L,

L tube Tand tube Eislled with liquid. I

then draw some liquidthrough draining cock P1, or, on the contrary, Iinayadd somein jar Rin order that thefliquid level in container r may beabout one centimeter below 'the lower end of tube b.y

Instead of proceeding as has just been de# scribed, I may furnish theapparatus with liquid iii a single operation by admitting liquid undersutliciently high pressure, for example by means of a container lyingabove the apparatus, through draining cock P2.

' The apparatus is thus furnished once for Aall and ready for operation.

I then put valve V1 into final communication with the container holdingthe gas to be analyzed and proceed with the measuring operations properas follows:

l. Admission of the gas to be analyzed.

VFor this purpose I shut valve V2 and leave valves V1 and V4 open, andvalve V3 shut. Thefgas to be analyzed circulates freely through buretteB and escapes through side rpipe t.

2. Samplemeasuring. I shut valves V1 and V* and open valve The operatinggas causes the liquid to rise within container i and traps the gas to beanalyzed in'buiette 3. Oxygen absorption. I open valve V2; the liquidflows on through burette B and tubes d and c, driving before it the gasto be analyzed which comes to be absorbed kin burette L in the presenceof thev copper; the liquid continues flowing on through tube T, valveV2, tube E and tube e and accumulates in reservoir F.

4. Residual gas measuring. I shut valve .V3 and open valve V4; theoperating gas n0 tain amount of liquid remaining suspended in the lowerpart of burette B owing to the presence of capillary tube b. With thecapillary tube illustrated iii the drawings referred to, the pressureunder which the residual gas is collected is, of course, belowatmospheric pressure. But the capillary tube might as Well be bentupwards and terminate higher than lthe bottoni of the measuring burette,for example ashigh as or even higher .than the top of the burette,provided its Open end be directed downwards so as to permit a convenientdipping into the container 1'. The pressure under which the residual gasis collected might in the latter cases be higher than atmosphericpressure.

directlly]7 from a suitable graduation which would e carried by buretteB the volume that would be occupied by the residual gas,`the latif.' :we

In all cases, it would be possible to read i neueren; Y 'Y i Y 3g terbeing broughtbackfto atmosphericpres.-V sure, fk but, in f practice,said residual volume Will be automatically" registeredL as `follows: Letit bethe height above the lower :end of `the liquid lwithin,barette BYlies,"hence, 7L corresponds.l ,touthe depression," measured as height ofthe Vliquidin the apparatus, under which the residual gas is collected.To this height hcorresponds a single, perfectlyrdetermined, level/X ofthe. liquid in tube E, Yand itis this level that Iin'dicate on arotaryregi-l istering cylinderggbyf means of aftrac'erv the movement ofwhich is controlled by theme-y vtionsof a :crystal oat lrestin-g'on thesurface of thegliquid withinitub'e EL .i Inorderto obtainac'curatemeasuring, itis cbyiously important'toprovide that a small variation ofthe residual'gas volume will cori respond toas large as possible avariation of height h and, consequently, off the ymotionzof the. iioat:that controls the registeringV device. orderto: achieve this result, Ihave onlyV to make tliefmeasuring. burette of as' small as l possibleasectiomwithout providing forl any capillary action, however, at theplace Where the liquid stops; 'and such visthe case' with the buretteshown by Figure 1:, Where, as already stated,. the residual volume isvery small;

about` 501% of the initial'` gas, I'fmerely have to kconstitute'themeasuring burette after the mannen shown, as anexample', by Figure 3,

' so thaty Aagain theliquid level; will lie inthe thinfpart of: theburette.V

- Similarly, Figure-4 corresponds to thev case Where'only a very-small;part of the gas is absorbed;

*'Ofcoursdrmy .invention applies :as Well tol the case olf' a :liquidthat is itself anrrab# sorbenttwithout havingto-fbe put vinthe pres'-thatzha'salsolthe eeetjofensuringan intimate Contact between theabsorbentand the gasltofbeanalyzed. Y if j y n lllyinvention isequallyapplicable inthe ence 'oan solid,v andfalso to the; ease: 'ofi abiysorpti'onxby ar solid-,.falone.w Inthe latter case', thev 'solid is putin 'I the absorption burette L, and. the' liqufidvvithfwhich the`apparatus is furnishedk is 4then merely an operating v liquid case; "off'analysis through combustion. The

' gas caused to be-circulate'd'through the'pmeas- 'uringffburette isthen obtainedibypreviously mixing,` inkIlQiWnplopDrtions, the gas to beanalyzed and a fuel gas Which will generally be oxygen. Combustioniseffected inside the burette lor reaction chamber L, suitably arrangedfor the. purpose, and the composition of theV initial gas is determinedfrom the measurement, carried outV as hereinabove explained, of thevolume of the residual gas imprisoned in burette Bi V' l claim as myinvention-:- I y v 1., The method of analyzing a gaseous mix- In thecase where the. proportion of` gas to `be absorbed is known' als being,for instance,

ture, whichscomprises; removing one or more constituents of a given;quantityV7 of they gaseous mixture'fby aj suitable treatment,enclosvingl theresidualfgasremainng after-.fsaid n n treatment Within a.container fwhichi termium tube eommunicatmg with atmospheric air inatesr at fits'lovver. end in an openy capillary and: atigits upper endin another capillary xtube, ,the extensionzof Which isa hydrostaticequilibrium tubecommunicatingfwith atmospheric air, allowing'hydrostatic equilibrium to take: place Within v'saidcontainerycapillary l tubes hydrostatic equilibrium theresidual,rvgasthereby enclosedV l Y '870 Y the.r lowerfpart 'of ytheffcentainerfand` theraet jacentycapillary'1tube,1.-.Wh:ile; the other.fills the capillary tube adjacenttofthe' upper-end of the containerandparti of the, hydrostatic equilibrium tube, and measuring? the height fof the liquidi enclosediwithinl thelowerzpart 2. Thefmethod offanalyzing rai gaseous mix*- v ture, which comprisesremovingone or more nconstituents. ci a givenl quantity oljthelgaseous.y mixture by asuitable treatment, enclos-` ing the; residual :gas remaining afterysaid treatment Witliinga `container which" term-i.'- natesat its lowerendl` 1n an oplerijcaprllary tube communicating with atmospherici airein 'llslthelower-ipart offV thecontainerandthe Y adj acent, capillarytube,- whilef the. other fills the capillary tube adjacenttotbe'upperend off the.. containerfandqpart et the` hydrostatic thev-liquid.Y enciosedf Within, the ascending branch ofthe; hydrostaticequ-i-libr'i-limfv tube.

' equilibriuml` tube,:and':measuning tliefheightof 3i. 'lfllielmethodfota-nalyzinga.zgaseousimixe K' ture, which comprises circulating thegaseous mixture-under adetermined pressure through p a;containerWhichfterminaiteslat itslowen end in an. open. capillary tube,trapping a deter'- mined volume .ofv the'1v gaseous mixture 4Within Ythe container, forWandingry said` volume through .another capillarytubeV to' a treatment chamber, removi'ngzoneror more .constituentsoffsaidvolume .byra suitable treatment taking place'. 'insider vsaidiVchamber, causing the` re meaning :gas *toV flow' backwards intov` thecon-- ta1ner, allowing hydrostatic equilibrium Vto take place Within fsaidicontainer, capillary f tubes', treatm'entf1 chamber and??hydrostatic equilibrium tube, the l*residual? gas` bei-ng 'f therebyenlosedbetvveen -t'Wo Y bodies off-"liqcontafiner# and? the; adj acentcapillary tube, Wlifiletheotheretillls the capi-liarytubeeatlja` a Y Y'1,850,311k

through a container which terminates at its .adeterminedvolume of thegaseous mixture lowerendby-an open capillary tube, trapping within thecontainer, forwarding said vol-- ums through another capillary 7tube* toak f treatment chamber removingV one or more constituents of saidvolumeby a suitable c treatment. taking ,placeinside 'said chamstaticequilibrium tu e.y

ber, causingthev remaining ygas to flow `haekvirards into.the-container, allowing hydrostatic equilibrium toy take place withinsaid container, capillary tubes, treatment chamber and hydrostatic euilibriunr tube, the residua-l gas being there y`enclosed between twobodies of liquid, one of which fills the vlower part of the containerandthe advjacentcapillarytube, lwhile the otherlls the capillary tubeadjacent to the upper end of the container, the treatment chamber andpart of the hydrostatic equilibrium tube, and measuring the height ofthe liquid enclosed wit-hin the ascendin branch of the hydro- 5. Anapparatusfor analyzing a gaseous mixture by removal ofone or moreconstituents of a given quantity of the gaseous mixture and measurementof the quantity of the residual gas remaining after said treatment,comprising -a `container for trapping said given quantityof the gaseousmixture, which container terminates at its lower end in an opencapillary tube communicating with atmospheric air, avchamber Jfortreating the given quantity of the gaseous mixture, a c apillary tuber,connecting the topy of saidy con-v tainerywith the-top of saidtreatment chamber, a hydrostatic equilibrium tube formino an extensionof the vtreatment chamber an means rfory circulating the gaseous mixturethrou h the container, trappinga given quantity o said mixture withinthe container, forwarding it into the treatment chamber, and expellingthe gas remaining after treatmentinto the container. c 6. The method ofanalyzing a gaseous mixture, which comprises collecting a sample of thegaseous mixture in a container between two bodies of liquid, `onecontacting withthe gaseousmixture'at the lowest-part of the spaceoccupied by the same, and the other at the highest part ofsaid space;forcing said gaseous mixture at least once into a ytreatment chamber bymeans of the firstnamed `liquid which flows downwardly through the gasin saidy treatment chamber;

removing oneor more constituents of the gaseous mixture; allowing theresidualgase'ous mixture to be transferred from the treatment chamber tosaid container; and determining the quantityof said residualgaseousmixture.

k7. The method of analyzincr a gaseous mixture, which comprisescollecting a sample of the gaseousy mixture in a container between twobodies of liquid, one liquid contacting with the rgaseous mixture at thelowest part of the space loccupied bythe same, and the other at thehighest part of the said space; forcing said gaseous mixture atleastonce Vintov a treatment chamber by means of the first-named liquid whichHows downwardlythrough the' gas inthe treatment chamber;

removing one or more constituentsV of the gaseous mixture; allowing theresidual gaseous mixture to be transferred from the treatinent chamberto said container; allowin a hydrostatic equilibrium to take place witinthe residual gaseous mixture and the two ,bodies of liquid; andindicating the height of the volume of the residual gaseous mixture inthe said container by the height of the second-mentioned'liquid ina'tube open to the atmosphere, which height difers from the height ofthevolume of the residual gas only by a constant quantity.

8. The` method of analyzing a gaseous mixture in a container whichcomprises collecting asainple of the aseous mixture between two bodiesof liquid, one liquid contacting with the gaseous mixture at the lowerpart of the space occupied by the same and the other at the highest partof the said space; forcing said gaseous ,mixture at least once into atreatment chamber by means of the first-named liquid which flowsdownwardly through the gas in the treatmentchamber; removing one or moreconstituents of the gaseous mixture; allowing the residual gaseousmixture to be transferred from the treatment chamber to theirst-mentioned container; allowing a hydrostatic equilibrium to takeplace withinthe residual gaseous mixture and *two bodies of liquid;indicating ythe height of the volume of the residual gaseous mixtureinVthe said container bythe height of the ysecond-ntientioned liquid in atube open to the atmosphere, which height differs from the height of theresidual gas only by a constant quantity; and Y registering the heightof the liquid in the said tube by means of a float following the saidheight.

-iIn testimonywhereof I aix my signature.

mman REN LoPoLD roman

